University of Pennsylvania

Department of Chemistry
Chemistry 221
Mid-Term Examination 1
Wednesday, Oct. 4, 2006
Since time is limited, use labeled diagrams and/or equations to illustrate your answers. TA's will be
looking for appropriate explanation and justification.
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1. (a) (9 pts) Explain with the aid of diagrams what is meant by the following terms:
(i) Black body radiation,

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(ii) Stefan-Boltzmann Law,

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(iii) Ultraviolet catastrophe.

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(b) (8) You are told that the wavelength of the n=3 → n=2 fluorescent transition of the hydrogen

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atom lies at 656 nm (Balmer Series). Calculate the wavelength corresponding to the (high-energy)
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convergence point of this series.
(c) (8) Suppose that light from an excimer laser at a wavelength 254 nm were incident on a metal
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surface having a work function of 2.0 eV. Calculate the maximum possible velocity (in m s-1) at
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which electrons could be ejected from the surface by the photoelectric effect.
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2. (a) (9) Write down in each case a simple quantum mechanical equation that explains what is
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meant by the terms:

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(i) probability density, (ii) average value, (iii) orthonormality.

(b) (8) Explain what is meant by the following terms:
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(i) variance
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(ii) quantum number

and explain how these may relate to the Heisenberg Uncertainty principle.
(c) (8) In Chapter 4, the book mentions a number of quantum mechanical postulates. State two of
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them in your own words, with a brief explanation and/or illustration.

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 3. (a) (9) The function ψn(x):

2  nπ x 
ψ n ( x) = sin  
a  a 

Is an eigenfunction of one of the following operators:

ℏ d ℏ2 d 2 ℏ ∂ ∂ 
; − + V ( x) ;  y −z 
i dx 2m dx 2 i  ∂z ∂y 
(i) Pick the correct operator and justify your choice.
(ii) What eigenvalue(s) would you generate by applying the operator you choose to the
given wavefunction?

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(iii) To what properties do the other two operators relate? Use a diagram or a mathematical

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expression in each answer.

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(b) (8) Explain what is meant by the term “degeneracy”. Give examples of two distinct types of

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quantum mechanical system that exhibit this behavior.
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(c) (8) Briefly explain the two following concepts, with the aid of diagrams:
(i) Classical turning point, as related to the quantum mechanical harmonic oscillator,
(ii) Quantum mechanical tunneling.
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4. (a) (6) Explain some similarities and differences between the eigenfunctions of the Hamiltonian
for a hydrogen atom and a diatomic molecule.
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(b) (5) Write down the general form of the Hamiltonian Operator for the 1-D Harmonic Oscillator.
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(c) (8) Draw one diagram for each case, describing the energy level structure for:
(i) A rigid rotor
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(ii) A harmonic oscillator.

Label each one in detail and point out the similarities and differences.
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(d) (6) With the aid of information at the end of the test, prove that the microwave transitions of a
h
molecule acting as a rigid rotor will be separated by the quantity: Hz.
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4π 2 I

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 Information
1 Debye (D) = 3.336 H 10-30 C m
Planck's Constant = 6.6262 H 10-34 Joule sec.
Boltzmann's Constant = 1.381 H 10-23 Joule K-1
Gas Constant = 0.08206 liter atmos mole-1 deg-1 = 8.314 Joule mole-1 deg-1
Velocity of Light in Vacuo = 2.9979 H 108 meter sec-1
Avogadro's Number = 6.022 H 1023 molecules mole-1
Charge of electron = 1.602 H 10-19 Coulomb
Mass of electron = 9.109 × 10-31 kg
1 eV / 8066 cm-1 / 96.485 kJ mole-1 ≡ 1239.5 nm

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1Å / 10-10 meter

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hc
E= Hψ = Eψ

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λ

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J ( J + 1)ℏ 2
EJ = = BJ ( J + 1)
2I
2π 5 k B
4
1 2 p2 n2h2
L = J ( J + 1) ℏ σ= = 56.7 nWm -2 K -4 Ek = mv = =
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15c 2 h3 2 2m 8mL2
Lz = ml ℏ
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E ( x, t ) = E0 cos ( ωt − kx )
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 Answers
1. (a) See notes.
(b) n=3 → n=2 has a frequency of 0.250 – 0.111 = 0.139 times the Rydberg constant. This is
equivalent to 656 nm. n=∞ → n=2 has a frequency of 0.25 times the Rydberg constant.
Therefore, the wavelength of the convergence limit is 0.139 / 0.25 × 656 = 364.7 (~365) nm.
TA’s should warn students who use too many decimal points, but not deduct at this stage
unless it is unreasonable.
(c) 254 nm ≡ 1239.5 / 254 × 96.485 = 470.8 kJ/mole ≡ 7.819 × 10-19 Joule per particle
2.0 eV = 2.0 × 96.485 = 192.97 kJ/mole ≡ 3.204 × 10-19 Joule per particle.
Excess energy = 4.615 × 10-19 Joule per particle = ½ mv2.

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4.615 ×10−19 × 2

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v= −31
= 1.01×106 m s -1
9.109 × 10

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2. (a)
(i) ψ *ψ

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(ii) Ω =
∫ψ *ψ dτ
(iii) ∫ψ i *ψ j dτ =δ i , j
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Comments: (i) Probability density is proportional to the square of the wavefunction as written.
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Normalization affects the form of this. One can also define it with reference to an interval dτ, so that
it can be rewritten: ψ*ψ dτ, in which case it gives the fractional probability that the particle will be
found in the spatial element dτ.
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(ii) The denominator should be included as a matter of practice. If ψ is normalized, the

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denominator is unity, by definition.

(iii) Note that we need two differently labeled functions, which could be the same if i=j. The δ
function is the Kronecker delta, which the students are supposed to know about.
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(b) (i) Variance (x) = σ 2 = x 2 − x

2
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The square root, σ, is identified with the standard deviation.

ℏ
The Heisenberg principle writes that σ xσ p ≥
2
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(ii) If something has a quantum number, this implies certain knowledge of some property, which is
then not subject to the Heisenberg uncertainty relation. If two such properties are expressed by
quantum numbers, those properties are considered to be well-defined, and can be known
simultaneously to an arbitrary precision.

(c) See Chapter 4 notes.

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 3(a) (i) The middle one, given that V(x) = 0 by definition for the model.
(ii)
n2h2
En =
8ma 2

(iii) The left one is for linear momentum along the x direction. eikx , for example.
The right one is for angular momentum along the x direction. Diagram of rotation in the y-z plane
with AM directed along the x-direction would be OK if correctly labeled.
(b) In a cubic PIB case, which is the one with which the students are probably the most familiar,
permutation of the same set of three quantum numbers (nx, ny, nz) give rise to a degeneracy if the
values of ni are not all the same. Some numerical values would be useful to illustrate the point.

In the rigid rotor, the different values of MJ have the same energy in the absence of an external field.

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This is a little different from the other case, since the quantum numbers have different significance.

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Still, this is known as a true degeneracy, where different values of MJ do not affect the energy.

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(c) See notes. Good diagrams needed.

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4. (a) Similarities: The 3-D Hamiltonian for the H-atom can be factored into a radial and angular
part . The radial part for a diatomic molecule is taken to be fixed. The angular parts of the
Hamiltonian are identical. It follows that the eigenfunctions for the angular parts are the same.
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Differences: The main difference is in the radial part, which occurs because of the different potential
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energy constraints placed on the system. In the case of H, we have a Coulomb term, whereas for the
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diatomic molecule, the potential energy term is factored out, since it is taken to be constant.

(b) Same as middle expression in 3(a), except replace the V(x) by ½ kx2 .
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(c) From notes. Focus on different spacing of energy levels between the two models. Answers for
either 2-D (in terms of just m) or 3-D (in terms of J or l) would be acceptable for rotation with
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appropriate explanation.
(d) Based on the diagram in 4(c), they should identify the transitions as being between adjacent
energy levels, and then mathematically show that the spacing is 2B. Then convert the expression to
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Hz.
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